Triphenylmethan dye and process of making same.



OF BERLIN, GERMANY.

TRIPHENY-LMETKAN DYE AND PROCESS OF MAKING SAME.

Speeifieatien f Letters Patent.

WILHELM lIEltZliEltG, OI" BERLIN, AND OSVi'AlrD SGfiARFE BERLIN, GERMANY, ASSIGNORS TO AC'TlEN (3E5 Application filed Ksreii 28 1907 Serial Ne- 865,206.

To all whom it may concern:

Be it knnwn that We, WILHELM Hnnznnne and 01+ WALD SCHARFEN in" no, subjects of the Emperur of Ger many, residing at Berlin, Germany, Hagelsberger- 5 strasse respectively, Schfineherg, near Berlin, Warthurgstrusse 9, have invented certain new and useful Improvements in Triphcnylmethan Dyes and Processosoi Making the Some, of which the following is a specification.

Our present invention relates to the manufacture 0i valuable dyestuffs of the triphimylmethan series, which dye wool in an acid bath clear green shades, by condensing an slkylbenzylunilin sulfonic acid with an arylsulionic other of an ortho-uxy-aldehyde cf the gen erul formula:

n c n cnoca,

in which R means a hydrogen atom or an alkyl group such he methyl or ethyl or another radical such as for instance chlurin, whereiis It means the residue of an arylsulionic acid such as for instance SO C H or SO,.(l H,.UH and then oxidizing the intermediate leuco-cmnpound. Thus for instance we condense the pnra-teluene sulfnnic ether of snlicyl ald ehyde'.

agent, such 8,5, for instance, sulfuric acid may be used;

and for oxidizing the new intermediate leuce-coinpound to the dyesluff, any suitable oxidizing agent may be employed.

As to the production of the nrylsulfonic others of the above given general iurmuln i. c. of the urylsulfunic others of sulicyl aldehyde or of uhoinnlugue or a. derivative then-oi such others may he obtained by acting aqueous solution of the sodium or potassium salt of the oxyhhlehyde in qnestien prefer-a1 ily while heating and agitating well. The pruductiun of such an other may for instance he as follows: 25 parts of su-licyl iil(l*li'il(: are dissolved in 250 parts 0! hot waler by means of 24 IRLIIS of caustic soda lye (40 Brunn specific gmvity}; while agitating well one adds 50 parts of pum-inluene sulioehlorid OH 1 11 50 11 (containing uhout 80 per cent, of pure snhstmwe), the ii-lupi-mture living kept at 70 tu 80 C. The rem-lion is finished if the yellow solution has (leculuiiZc-d, the chlurid then being ahiiurbcd. The mass is ullo..-..d to cool while stirring with an nrylsulfunic vhlnrid: ltSO il upon the l l l NBERQ, 01" SCHONEBERG, NEAR ELLSOHAFT FUR ANILIN FABRIKATiON,

Patented Sept. 1'7; 1907.

well, thus the reaction product, which previously seping.

sister: in a resinous form, solidiiying to small white spheres. It is isolated by filtering, washing and dry- Aceording to the above given method of preparing the para-toluenosulionic ether of salicyl aldehyde the corresponding others of a homologue or of derivatives 01 salicyl aldehyde can be obtained. In the following table the characteristic features i some of these new compounds may be seen.

. Melts crystallizes Body Fm at from ligroin in 5 P-tolueriesnlio- OSO G H CH 5&60 Pris m s a r 4 sulieyl-akle' I ranfed in hyde. (3H0 stnrike bundies.

P-teinenesulfoo-lmmosal i cyl-uldehyde.

P-tolne ncsnlfnpin am on a ll eylhldeh yde.

Benzenesuliop-hnrnoanlicyl-aldehyde.

CHO

Oil,

These products are insoluble in (mid water and very Fill diflicultly soluble in hoiiing water.

Newin carrying out the process wlfich forms the subject matter 0i our pri sent invention, the following examples may be given, the parts being by weight.

Example. Dyestufl derived from the para-toluene- Rh um bli ke small leaves.

' Needles ar ran ed in bum cs.

sulionic ether of salicyl aldehyde and ethylhcnzylaiiilinsuli'enic acid.

In a mixture (if 90 parts of water and pans of alcohol are dissolved 28 parts oi paratiiluenesuliesalicyl aldehyde and 58.2 parts of ethylhonzylunilinsulinnic acid with the additionbi 10 parts oi concentrated sulfuric acid; the mass is then heated to boiling until the aldehyde has disappeared. After distilling oh the alt-ehel, the residue is poured into 500 arts of watmwhereby the product of the reaction,

namely the lencudisulionic acid is separated, while the mixture is hot, as a white resin, which orifceoiing solidiiiifi in a. short time. In order to oxidize the leuco-disnli'onic acid thus obtained, 84 parts of it are dissolved in about 1600 parts of water with aid of ii parts of calcined sodium carbonate; to this solution are i added while stirring well 75 parts of a paste of lead l peroxid, containing 32} per cent of IbU whereaiter tit) parts of acetic acid (30% strength) are allowed to i run in. The oxidation being finished, the lead is separated from the solution by addition of the calculated quantity of sulfuric acid; after filtration the dyostuff is separated from the iiltrate by addition of Glaubers salt. it is filtered and dried. The new dyenlLllli is thus obtained in the iorm ofa masshavinga eonpory luster it dyes wool in an acid bath clear green tints which are satisfactorily fast to washing.

it is obviousjhut our present invention is; not limited to the foregoing example or to the details given there ether of salicyl aldehyde the para-toluenesulfoi of para-homosalicylaldehyde (compare 3 ii the manner described in the foregoing c .nple, a dyestui'f is obtained which resembles very uuch the dyestuif obtained according to this example. it yields on wool in an acid bath green tints which are somewhat more yellow than those obtained with the dyestuii oi' the foregoing example. l urtliernioreif the para-t ll uene-sulfenie ether of orthtthoinosaiicyl adiohyde (compare 2 in the foregoing table), be converted into a leuco-disuli'onie acid by joint oxidation with ethylbenzyl-anilinsulionic llild and the leuco-eonipourul be oxidized to the dyestul'f, a dyestnff is obtained which also dyes woolin an acid hath green tints. it may also be stated that. the dyestuffs which can hrobtained according to the present invention very much resemble each other in their physical and chemical qualities. in water they dissolve to a green solution; in alcohol they are soluble partially in the cold and totally on boiling, the solution thus obtained showing ngrecn tint. On addition oi' caustic soda lye or hydrochloric acid to the aqueous solution green flakes separate. In concentrated sulfuric ili'ltl thedyestui'is dis solve to a yellow-brown solution, the color of which on addition of ice turns to gn-en.

It is obvious that. instead of the liztiutolueln-sulionh' other other uryl-suli'oniiothers, such us lor instance the others of lmnzene sulionie zu'id lilil) he used; lilw- 1 wise, for the ethylbenzyluniliusuli'oniracid, used in t the foregoing example nit-thylbenzyhiuilinsuiionie the foregoing specilicution'io form a leucnileliued disulfonle acid, and then oxidizing the intermediate ieuco compound.

2, As new articles of manufacture the new dyestuiIs 0f the li'lplltrllilllti'lliiiil series width may he obtained by ronileusina' un ulkylhenzylunliiu sulfonle acid with an ill'ylsuli'onie ether of un oxynldehyde having the general i'oriuulu V detineu in the foregoing specification and then oxidizing ilit' iniel'tn tlizitc leuro-i'onIpOund, which rlycstulis dye wool in nu ui'id huth clcur green tints which are satisfactorily lusl to \mshiue, these dyeslulfs dissolving in water to a green solution, from which solution on addition of caustic Mdlil lye or oi hydrochloric acid green flakes separate, and being soluble in alcohol namely partially in the cold and lolnlly on lioiling, the solution thus obtained showing :1 green lilil, und which dyestuffs in concentrated sulfuric will dissolve to u yellow-brown solution, the color oi whic on nihliliou of lo,- turns to green.

2:. .\s it new article of manufacture the new dyestuif of the tripiu-nylluethan series which may he obtained by con- (lensing elnylM-nzylunilin sulfonlc acid with the para iohu-nesull'onlr ether of saiicyl aldehyde and oxidizing the interinmiiule hwot-ompound, which dye-stuff dyes wool in illi urid hnih u eh-ur green tint which is satisi'nrlorily fast to wishing. this dy siuli' dissolving in water to a green snlllliun from which solulion on addition of enustir' soda Lnor of hydrovhlorir nrid green ilukes separate, and this dyesluft' living soluble in ulvnhol. namely partially in the (old and lolnlly on limiting, the solution thus ohiuined -sho\\'in; u green tint and which ILH'slttCF in concentrated 

